US20110280765A1 - Steriliser with exhaust gas cleaning system for decomposing nox with ozone - Google Patents

Steriliser with exhaust gas cleaning system for decomposing nox with ozone Download PDF

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Publication number
US20110280765A1
US20110280765A1 US13/145,977 US201013145977A US2011280765A1 US 20110280765 A1 US20110280765 A1 US 20110280765A1 US 201013145977 A US201013145977 A US 201013145977A US 2011280765 A1 US2011280765 A1 US 2011280765A1
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Prior art keywords
gas
sterilizing
chamber
exhaust
ozone
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Abandoned
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US13/145,977
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English (en)
Inventor
Tomoyuki Hirose
Ryuichi Iwasaki
Kazuhiro Kimura
Shigeki Okumura
Kiyotaka Arai
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Noxilizer Inc
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SAIAN CORP
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Assigned to SAIAN CORPORATION reassignment SAIAN CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ARAI, KIYOTAKA, HIROSE, TOMOYUKI, IWASAKI, RYUICHI, KIMURA, KAZUHIRO, OKUMURA, SHIGEKI
Publication of US20110280765A1 publication Critical patent/US20110280765A1/en
Assigned to NOXILIZER, INC. reassignment NOXILIZER, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SAIAN CORPORATION
Abandoned legal-status Critical Current

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
    • A61L2/20—Gaseous substances, e.g. vapours
    • A61L2/202—Ozone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/02—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using physical phenomena
    • A61L2/14—Plasma, i.e. ionised gases
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
    • A61L2/20—Gaseous substances, e.g. vapours
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2202/00—Aspects relating to methods or apparatus for disinfecting or sterilising materials or objects
    • A61L2202/10—Apparatus features
    • A61L2202/12—Apparatus for isolating biocidal substances from the environment
    • A61L2202/122—Chambers for sterilisation
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2202/00—Aspects relating to methods or apparatus for disinfecting or sterilising materials or objects
    • A61L2202/10—Apparatus features
    • A61L2202/13—Biocide decomposition means, e.g. catalysts, sorbents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2202/00—Aspects relating to methods or apparatus for disinfecting or sterilising materials or objects
    • A61L2202/20—Targets to be treated
    • A61L2202/24—Medical instruments, e.g. endoscopes, catheters, sharps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/10—Oxidants
    • B01D2251/104—Ozone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/404—Nitrogen oxides other than dinitrogen oxide

Definitions

  • the present invention relates to a sterilizing apparatus used for medical instruments such as scissors and catheters for medical use and other items to be sterilized that require increased sterilizing reliability, an exhaust system incorporated into the sterilizing apparatus, and a sterilization method performed by using the sterilizing apparatus.
  • a gas sterilization means for killing such as bacteria and viruses present on an item to be sterilized has been widely used in which an item to be sterilized such as medical instruments is contained in the atmosphere of a sterilant gas such as nitrogen oxide (hereinafter, also simply referred to as “NOx”), ozone, and H 2 O 2 for a certain time period.
  • a sterilant gas such as nitrogen oxide (hereinafter, also simply referred to as “NOx”), ozone, and H 2 O 2 for a certain time period.
  • NOx nitrogen oxide
  • ozone ozone
  • H 2 O 2 H 2 O 2
  • a treatment method has been employed by which the sterilant gas is removed by using an oxidant for converting NO into NO 2 and an absorbent for collecting NO 2 .
  • concentrations of NO, NO 2 , and NOx can be decreased to the LTWA level (Japanese Unexamined Patent Publication No. 521118/2007).
  • an exhaust gas is purified by circulating the exhaust gas multiple times in a gas processing tank which is filled with an adsorbent such as activated charcoal, water, and dilute nitric acid, or a thermal catalytic agent to adsorb ethylene oxide gas (Japanese Unexamined Patent Publication No. 312709/2000).
  • an adsorbent such as activated charcoal, water, and dilute nitric acid, or a thermal catalytic agent to adsorb ethylene oxide gas
  • a so-called SCR method has been employed in which an SCR catalytic agent is provided in an exhaust passage of an engine, and a reducing agent feeding apparatus for supplying a reducing agent such as ammonia is provided at the upstream side of the SCR catalytic agent to reduce NOx in the exhaust gas with ammonia supplied from the reducing agent feeding apparatus by a catalytic action of the SCR catalytic agent (Japanese Unexamined Patent Publication No. 303826/2000).
  • the present inventors invented a high concentration NO 2 generating method which has been filed in another patent application, and has developed a sterilizing apparatus with substantially increased reliability by using a high concentration NO 2 gas obtained by the above method.
  • an exhaust gas exhausted from the sterilizing apparatus contains a high concentration NO 2 gas
  • the exhaust gas cannot be made to be harmless to a safe level within a predetermined time by any of the conventional methods and apparatus for processing NOx.
  • the sterilizing apparatus using the high concentration NO 2 gas cannot be practically used in such as medical sites.
  • the present invention aims to provide an exhaust system which can efficiently and reliably purify a high concentration NO 2 exhaust gas having a concentration beyond the normal level.
  • the exhaust system of the present invention is an exhaust system for exhausting an exhaust gas used for sterilizing an item to be sterilized by using a high concentration NO 2 gas, including an ozone generator, a gas treatment means for adsorbing ozone generated by the ozone generator and NO 2 in the exhaust gas and accelerating generation of dinitrogen pentoxide or nitric acid by a reaction of the ozone and NO 2 to retain the resultant, and an exhaust apparatus for exhausting the exhaust gas.
  • the present invention is an exhaust system for exhausting an exhaust gas used for sterilizing an item to be sterilized by using a high concentration NO 2 gas, including an ozone generator, a gas treatment means for adsorbing ozone generated by the ozone generator and NO 2 in the exhaust gas and accelerating generation of dinitrogen pentoxide or nitric acid by a reaction of the ozone and NO 2 to retain the resultant, and an exhaust apparatus for exhausting the exhaust gas.
  • the ozone generator includes an ozonizer and an ozone chamber for storing ozone generated by the ozonizer.
  • a buffer portion for adjusting a mixture ratio of NO 2 in the exhaust gas and ozone is further provided at an upstream side from the gas treatment means.
  • the gas treatment means uses an adsorption catalyst.
  • the exhaust apparatus exhausts the exhaust gas used for sterilization in multiple times.
  • the present invention is a sterilizing apparatus including the following configuration.
  • the sterilizing apparatus includes (a) an NO 2 gas supply system configured by a circulating path in which a chamber for storing a high concentration NO 2 gas, a plasma generator, and a circulating means are connected, (b) a sterilizing chamber connected to the chamber via a first open/closure device, and (c) the exhaust system connected to the sterilizing chamber via a second open/closure device.
  • the chamber is connected to the exhaust system via a third open/closure device.
  • the sterilizing chamber is provided with a measuring path for returning the high concentration NO 2 gas in the sterilizing chamber to the sterilizing chamber through an NO 2 sensor.
  • a plurality of sterilizing chambers is connected to a single exhaust system.
  • the present invention is a sterilizing method using the sterilizing apparatus, wherein in a gas exhausting step for exhausting a high concentration NO 2 gas used for sterilizing an item to be sterilized, the high concentration NO 2 gas is exhausted to the exhaust system in part with a predetermined NO 2 gas contents.
  • a sterilizing method using the sterilizing apparatus wherein in a gas exhausting step for exhausting a used high concentration NO 2 gas after a sterilizing step for sterilizing an item to be sterilized, a procedure of exhausting the high concentration NO 2 gas in the sterilizing chamber to the exhaust gas treatment means by an exhaust apparatus of the exhaust system to obtain a negative pressure in the sterilizing chamber while the first open/closure device is closed and the second open/closure device is open, and subsequently, sucking the high concentration NO 2 gas remaining the chamber into the sterilizing chamber by the negative pressure by opening the first open/closure device and closing the second open/closure device is repeated.
  • the present invention is a sterilizing method using the sterilizing apparatus, including the steps of (d) setting an item to be sterilized in the sterilizing chamber (setting step), (e) vacuuming the inside of the sterilizing chamber (vacuuming step), (f) humidifying the inside of the sterilizing chamber (humidifying step), (g) opening the first open/closure device to supply the NO 2 gas generated by the NO 2 gas system and stored in the chamber to the sterilizing chamber (supplying step), (h) filling the dried gas mixture in the chamber (air charging step), and (i) generating NO 2 gas by driving the NO 2 gas supply system (circulating step), wherein the steps (g) to (i) are repeated a plurality of times.
  • a step of closing the first open/closure device and opening the third open/closure device to directly couple the chamber and exhaust system to exhaust the NO 2 gas remaining in the chamber with the exhaust system and to vacuum the chamber is performed.
  • FIG. 1 is an explanatory view illustrating a configuration of the exhaust system according to one Embodiment of the present invention.
  • FIG. 2 is an explanatory view illustrating a plasma generating portion in a configuration of the exhaust system according to one Embodiment of the present invention.
  • FIG. 3 is an explanatory view illustrating a plasma generator in a configuration of the exhaust system according to one Embodiment of the present invention.
  • FIG. 4 is an explanatory view illustrating an exhaust system according to one Embodiment of the present invention.
  • the exhaust system is a system by which an exhaust gas used for sterilizing an item to be sterilized with a high concentration NO 2 gas is exhausted.
  • the system is employed in a sterilizing apparatus which is capable of efficiently perform sterilizing process on medical instruments and other items to be sterilized.
  • an Embodiment of the sterilizing apparatus is described first.
  • a sterilizing apparatus is illustrated, the apparatus being configured to include an NO 2 gas supply system for generating a high concentration NO 2 gas, a sterilizing chamber for sterilizing an item contained to be sterilized with the high concentration NO 2 gas, and an exhaust system for making an exhaust gas which is the high concentration NO 2 gas used for sterilization to be harmless.
  • the NO 2 gas supply system includes a circulating path 4 connecting a chamber 1 , a plasma generator 2 , and a circulating means 3 .
  • the circulating path 4 is configured to include the chamber 1 , a flow resistive portion 5 connected to the chamber 1 at the downstream side of the path via a pipe, the plasma generator 2 connected to the flow resistive portion 5 at the downstream side of the path via a pipe, and the circulating means 3 connected to the plasma generator 2 at the downstream side of the path via a pipe.
  • the circulating means 3 is further connected to the chamber 1 at the upstream side of the path via a pipe such that a cyclic circulating path 4 is formed by the chamber 1 , flow resistive portion 5 , plasma generator 2 , and circulating means 3 .
  • a gas mixture including nitrogen and oxygen circulates in the circulating path 4 to generate NO 2 .
  • a gas including nitrogen and oxygen which is supplied from the outside to the high concentration NO 2 generating system as an ingredient is referred to as a gas mixture
  • a gas including NOx which is generated by circulating through the plasma generator 2 at least once is referred to as an NOx gas mixture
  • a gas which reached a desired level of NO 2 concentration by repeating the above-described circulation is referred to as a high concentration NO 2 gas.
  • the chamber 1 is an airtight compartment for containing high concentration NO 2 gas to be generated.
  • the chamber 1 has a rectangular box shape in the present Embodiment, however, it may have a spherical shape or cylindrical shape. Since the chamber 1 of the present Embodiment forms the circulating path 4 , a flow outlet, a flow inlet, and an openable and closable gas supply opening for taking out high concentration NO 2 are formed.
  • the flow resistive portion 5 is formed by an orifice 5 a .
  • the orifice 5 a is provided in the pipe at the downstream side from the chamber 1 , and makes up an orifice fluid meter. In the present Embodiment, therefore, it is advantageous that the flow volume of the gas circulating out of the chamber 1 can be measured.
  • the flow resistive portion 5 may be configured in such a manner that a portion of the pipe at the downstream side from the chamber 1 is configured by a narrow pipe to increase the flow resistivity of that portion.
  • the plasma generator 2 is a unit capable of generating a plasma under normal temperature and normal pressure by using microwaves, and is generally configured to include a microwave generating apparatus 2 a for generating microwaves with a predetermined wavelength, a waveguide 2 b which is connected to the microwave generating apparatus 2 a to transmit the microwaves, and a plasma generating portion 2 c which is provided integrally with the waveguide 2 b.
  • the microwave generating apparatus 2 a generates microwaves at 2.45 GHz, for example, and transmits the microwaves into the waveguide 2 b .
  • the microwave generating apparatus 2 a therefore, includes a microwave generating source such as a magnetron for generating microwaves, an amplifier for adjusting the power of the microwaves generated at the microwave generating source to a predetermined power intensity, and a microwave transmitting antenna for emitting the microwaves into the waveguide 2 b .
  • a microwave generating source such as a magnetron for generating microwaves
  • an amplifier for adjusting the power of the microwaves generated at the microwave generating source to a predetermined power intensity
  • a microwave transmitting antenna for emitting the microwaves into the waveguide 2 b .
  • an apparatus of a continuous variable type which is capable of outputting microwave energy between of 1 W and 3 kW, for example, is suitable.
  • the waveguide 2 b is made of a nonmagnetic metal (such as aluminum), for example, has a tubular shape with a rectangular cross section, and transmits the microwaves generated by the microwave generating apparatus 2 a toward the plasma generating portion 2 c .
  • the waveguide 2 b of the present Embodiment is configured by a square tubular assembly using top and bottom plates, and two side plates made of metallic flat plates. In addition to such plate assembly, the waveguide may also be formed by such as extrusion or bending process of a plate member. Moreover, a waveguide 2 b with an oval cross section may be used in addition to the waveguide 2 b with a rectangular cross section. Furthermore, not only by nonmagnetic metals, but the waveguide may be configured by various members having the waveguide property.
  • the waveguide 2 b is grounded in the present Embodiment.
  • the plasma generating portion 2 c is integrally configured with the waveguide 2 b , and includes a rod-shaped conducting shaft 2 d inserted through the waveguide 2 b and a tubular conducting tube 2 e .
  • the conducting shaft 2 d is further configured by an antenna portion 2 f which is inserted into the waveguide 2 b to receive the microwaves, and a center electrode 2 g protruding externally from the waveguide 2 b which, in the present Embodiment, is inserted through the waveguide 2 b via an electric insulator.
  • the conducting shaft 2 d of the present Embodiment has a circular cross section, however, the conducting shaft with an elliptical, oval, or a long oval cross section may be employed.
  • the conducting shaft 2 d of the present Embodiment is formed by using titanium, however, materials capable of conducting microwaves such as titanium alloy, copper, platinum, gold, and silver may be used.
  • a shielding film 2 h made of ceramic is formed at a tip of the conducting shaft 2 d (center electrode 2 g ) for preventing arc discharge and protecting the electrode.
  • the conducting tube 2 e has a generally cylindrical shape, and the inner diameter thereof is formed to be larger than the outer diameter of the conducting shaft 2 d .
  • the conducting tube is provided to cover the center electrode 2 g protruding externally from the waveguide 2 b while having the center electrode at the center, and a ring-shaped space 2 i is formed between the center electrode 2 g and conducting tube 2 e .
  • the base end of the conducting tube 2 e is electrically conductive and fixed relative to the waveguide 2 b , and the conducting tube 2 e is thus grounded via waveguide 2 b .
  • the conducting tube 2 e may have such as a rectangular cross section or an oval cross section in addition to a circular cross section.
  • a tip thereof is formed to have a length which terminates with substantially the same position as a tip of the center electrode 2 g .
  • the conducting tube 2 e of the present Embodiment is made using stainless steel, however, it may be made of such as aluminum.
  • a ventilation opening is provided at a position toward the base end thereof.
  • the circulating path 4 connecting from the flow resistive portion 5 to the plasma generator 2 is configured.
  • the gas mixture flowing in the circulating path 4 moves through inside the ring-shaped space 2 i toward the end of the center electrode 2 g .
  • a ceramic shielding tube 2 k is inserted to prevent the arc discharge relative to the center electrode 2 g .
  • the outside edge of the shielding tube 2 k is connected to the pipe 2 j directing further toward the downstream of the path to thereby form the circulating path 4 .
  • the microwave generating portion 2 c thus configured, 2.45 GHz of microwave (power is adjustable) generated from the microwave generating apparatus 2 a (magnetron) is emitted from the microwave transmitting antenna of the microwave generating apparatus 2 a provided at one end of the waveguide 2 b to the plasma generating portion 2 c .
  • the emitted microwave transmits in the waveguide 2 b and is received by the antenna portion 2 f of the conducting shaft 2 d in the plasma generating portion 2 c .
  • the microwave thus received by the antenna portion 2 f transmits on the surface of the conducting shaft 2 d , and reaches the tip of the center electrode 2 g .
  • the tip of the center electrode 2 g is electrically coupled to the waveguide 2 b , and is disposed nearby the tip of the conducting tube 2 e of a ground potential.
  • an intense electric field is formed between the tip of the conducting tube 2 e and the tip of the center electrode 2 g , especially in the vicinity of the tip of the center electrode 2 g .
  • the conducting shaft 2 d is formed to have a resonance point in the 2.45 GHz band, such that an intense electric field is efficiently formed at the tip portion of the center electrode 2 g.
  • nitrogen and oxygen of the gas mixture in the vicinity of the end of the center electrode 2 g generate dielectric breakdown by being excited through the intense electric field formed by the microwaves, and are displaced from the molecular state to the low-temperature plasma (non-equilibrium plasma) state.
  • the gas under the low-temperature plasma state has a high reactivity with respect to other gases under the low-temperature plasma state or molecular state. Therefore, when the gas mixture including primarily nitrogen and oxygen is introduced to the plasma generating portion 2 c , a portion thereof is converted to nitrogen oxides of such as nitrogen monoxide and nitrogen dioxide or to ozone.
  • the NOx gas mixture including NO 2 thus generated circulates through the circulating path 4 or is retained in the chamber 1 .
  • nitrogen monoxide generated according to equation 1 reacts stepwise with oxygen in the NOx gas mixture or with the ozone generated according to equation 3, and is further converted to nitrogen dioxide as shown in equations 5 and 6.
  • the NO 2 concentration increases.
  • Ozone generated according to equation 3 reacts with nitrogen in the NOx gas mixture to generate nitrogen monoxide.
  • This nitrogen monoxide is also converted to nitrogen dioxide by the reactions according to equations 5 and 6.
  • the concentration of nitrogen dioxide gradually increases and the high concentration NO 2 gas with a desired level of NO 2 concentration is obtained.
  • the generated nitrogen monoxide or nitrogen dioxide again passes through the plasma generator 2 , a phenomenon occurs that a portion thereof again becomes under the low-temperature plasma state by a dissociation reaction and thus returns to nitrogen or oxygen. Accordingly, when the concentration of the NOx gas mixture reaches a certain level of the high concentration NO 2 gas by repeating the circulation, the generation of nitrogen oxide and the dissociation of nitrogen oxide fall under an equilibrium state, so that the enhancement does not proceed further at a certain concentration.
  • a circulating path 4 including a single plasma generator 2 is illustrated as shown in FIG. 1 .
  • two or three or more plasma generators 2 may be connected in parallel to form the circulating path 4 . This is preferable since the high concentration NO 2 gas can be generated in a short time in such case.
  • the circulating path 4 may be divaricated in the plasma generator 2 to provide a plasma generating portion 2 c for each of the diverged paths.
  • the circulating means 3 is configured by using a pressure device 6 in the present Embodiment.
  • a fan may also be used as the circulating means 3 .
  • an air pump may be preferably employed, and an air blower or air compressor may also be used.
  • the air pump a diaphragm pump with approximately 20 to 100 watt power and made of fluorine rubber, a plunger pump made of ceramic, or bellows pump may be employed.
  • the pressure device 6 is provided in the pipe for connecting the plasma generator 2 and the chamber 1 , and is connected to apply pressure to the chamber 1 side at the downstream side of the path.
  • the high concentration NO 2 gas generating system of the present Embodiment makes up the cyclic circulating path 4 by connecting the chamber 1 , flow resistive portion 5 , plasma generator 2 , and pressure device 6 , in circular via the pipes.
  • the pressure device 6 By the operation of the pressure device 6 , the air (gas mixture) introduced from the inlet portion 7 flows through the circulating path 4 , and the NOx gas mixture is generated which includes nitrogen monoxide and nitrogen dioxide generated by the reaction of nitrogen and oxygen displaced to the low-temperature plasma (non-equilibrium plasma) state when passing through the plasma generator 2 .
  • the nitrogen monoxide is converted to nitrogen dioxide when it reacts with oxygen in the NOx gas mixture and ozone stepwise.
  • the high concentration NO 2 gas can thus be generated by the gradual increase in the concentration of the nitrogen dioxide.
  • an NO 2 concentration measurement sensor 8 is provided at the downstream of the chamber 1 . With this, the concentration of NO 2 can be measured.
  • a gas drying means 9 for adjusting a dew point of the air to be introduced in the chamber 1 .
  • the gas drying means 9 a self-regenerating system by means of molecular sieve filled in two tubes may be used, for example.
  • the chamber 1 is provided with pressure meter 1 a and plasma generator 2 is provided with pressure meter (not shown), respectively. With those, pressures in the chamber 1 and plasma generator 2 can be controlled, and it is possible to check if the pressure is abnormal.
  • the sterilizing chamber 10 constitutes a main portion of the sterilizing apparatus for medical instruments, and includes an opening for loading and unloading an item to be sterilized, a shielding door capable of sealing the opening, a gas supply opening for introducing a high concentration NO 2 gas, and a gas exhaust opening for exhausting an exhaust gas after sterilization.
  • the shielding door is provided with a sealing material in the periphery for securing the sealing property.
  • fluorine-containing elastomer is used from the perspective of the pressure tightness and corrosion resistance. It is preferable that the safety is improved when the shielding door is provided with an interlock which does not allow opening the door in the case an NO 2 gas concentration in the sterilizing chamber 10 is equal to or more than the level harmful for humans.
  • a supply pipe 10 a is provided from the gas supply opening to the chamber 1 of the NO 2 gas supply system.
  • the high concentration NO 2 gas stored in the chamber 1 passes through the supply pipe and is supplied from the gas supply opening to the sterilizing chamber 10 .
  • the supply pipe is provided with a first open/closure device 10 b using an air drive valve, and the supply of the high concentration NO 2 gas to the sterilizing chamber 10 is controlled by an on/off control of the first open/closure device 10 b.
  • the sterilizing chamber 10 is provided with a measuring path which sucks the NO 2 gas in the chamber by a pump to measure the concentration thereof with an NO 2 sensor 11 and returns the gas to the sterilizing chamber 10 .
  • the path is diverged into two paths in the middle to respectively provide two NO 2 sensors 11 a , 11 b for high concentration measurement and low concentration measurement such that measurements of the concentration can be performed with high accuracy.
  • the exhaust system 12 makes the high concentration NO 2 gas after a sterilization process (exhaust gas) and filled in the sterilizing chamber 10 to be harmless for exhaustion.
  • the exhaust system is configured to include an ozone generator 13 , a buffer portion 14 for adjusting a mixture ratio of ozone supplied from the ozone generator 13 and the exhaust gas, a gas treatment means 15 , an ozone treatment means 16 , and an exhaust apparatus 17 .
  • a dehumidifying portion D 1 and an exhaust gas flow meter F 1 In the downstream from the exhaust apparatus 17 and the upstream of the buffer portion, it is configured to include a dehumidifying portion D 1 and an exhaust gas flow meter F 1 .
  • the dehumidifying portion D 1 is composed of silica gel in the present Embodiment.
  • Silica gel serves to prevent a failure of the exhaust gas flow meter due to the dew drop inside the meter and promote efficiency of the gas treatment means 15 in the downstream by adsorbing the moisture included in the high concentration NO 2 gas (exhaust gas). It is noted that a portion of NO 2 is absorbed by the silica gel.
  • the exhaust gas flow meter F 1 measures the flow volume of the exhaust gas to be exhausted.
  • the ozone generator 13 includes an ozonizer 18 , an ozone chamber 19 , an ozone exhaust apparatus 20 , and an ozone flow controller 21 .
  • the ozonizer 18 (ozone generator) is an apparatus for applying a high voltage between electrodes provided with dielectric to discharge the air or oxygen filled in a discharge gap to convert the air or oxygen to ozone. Ozonizers are widely used as environmental equipments.
  • the ozone chamber 19 is a small space having a container form with approximately 40 to 80 L volume, and is connected to the ozonizer 18 to temporarily store ozone generated by the ozonizer 18 .
  • dinitrogen pentoxide generated by a chemical reaction with the high concentration NO 2 gas or ozone required for nitrification can be supplied by a low-powered ozone generator 13 such that the high concentration NO 2 gas can be securely made to be harmless.
  • the exhaust volume of ozone from the ozone chamber 19 is adjusted by the ozone exhaust apparatus 20 and the ozone flow controller 21 .
  • the ozone flow controller 21 is a regulating valve which can control the flow volume of ozone based on the flow volume of the exhaust gas measured by the exhaust gas flow meter F 1 .
  • the flow volume of the high concentration NO 2 and the mixture ratio of the ozone flow can be adjusted, and sufficient ozone relative to NO 2 included in the exhaust gas can be delivered.
  • the buffer portion 14 is a small space having a container form with approximately 10 L volume.
  • an amount of ozone being supplied fluctuates to fall in either an excessive or a short side relative to a time axis.
  • the amount of ozone being supplied with large fluctuations can be averaged by controlling the flow volume of ozone from the ozone chamber 19 with the ozone flow controller 21 on the basis of the exhaust gas flow meter F 1 and feeding the ozone to the buffer portion 14 for mixing, and by retaining the gas mixture in the buffer portion 14 .
  • the gas treatment means 15 is configured by providing a processing portion containing an adsorption catalyst on the exhaust gas path located at the downstream side from the buffer portion 14 .
  • the adsorption catalyst is a catalyst for excellently adsorbing NO 2 and ozone, and accelerating the reaction of the adsorbed NO 2 and ozone to chemically convert to N 2 O 5 , or generating HNO 3 by a reaction of NO 2 with remaining vapors.
  • zeolite is used as an adsorption catalyst. Of zeolite, silicalite is preferably used since NO 2 can be efficiently adsorbed.
  • the ozone treatment means 16 is located at the downstream from the gas treatment means 15 and serves as an ozone decomposition apparatus for decomposing the excess ozone in the reaction with NO 2 . With this arrangement, ozone can be exhausted by controlling its concentration to be a predetermined level or below.
  • the gas treatment means 15 thus configured adsorbs the gas mixture in which NO 2 and ozone are adjusted to be at a suitable mixture ratio in the buffer portion 14 , and chemically converts the gas to N 2 O 5 by NO 2 and ozone, or accelerates the generation of HNO 3 by the reaction of NO 2 and remaining vapors. NO 2 in the exhaust gas is thus removed, and the exhaust gas is made to be harmless.
  • NO 2 since NO 2 is eliminated by generating N 2 O 5 or HNO 3 by the chemical reaction with ozone, NO 2 can be efficiently eliminated even if the concentration of NO 2 is high. In sterilizing apparatus using high concentration NO 2 , reliable exhaust gas treatment can be performed within practically suitable time period.
  • an NO 2 sensor and ozone sensor are provided at the downstream side from the ozone treatment means 16 to check whether the exhaust gas has been made to be harmless.
  • a suitable mixture ratio of NO 2 and ozone in the gas mixture present in the buffer portion 14 is considered to be 2:1.
  • the mixture ratio of NO 2 and ozone in the gas mixture is thus made to be such that the ratio of ozone is larger than 2:1, and the mixture ratio is preferably 2:1 to 1:2, for example. In the present Embodiment, the ratio is 3:2.
  • the exhaust system thus configured is connected to the gas exhaust opening of the sterilizing chamber 10 by an exhaust pipe 22 therebetween. More specifically, the exhaust pipe 22 extending from the sterilizing chamber 10 is connected to the buffer portion 14 such that the exhaust gas exhausted from the sterilizing chamber 10 is transferred to the buffer portion 14 . Furthermore, the exhaust pipe 22 is provided with a second open/closure device 23 using an air drive valve, and the transfer of the exhaust gas to the buffer portion 14 is controlled by the on/off control of the second open/closure device 23 .
  • the exhaust apparatus 17 serves to suck the exhaust gas remaining in the sterilizing chamber 10 and transfer the gas to the exhaust system, and after making the gas to be harmless by the gas treatment means 15 , imparts energy to the flow of the exhaust gas by using such as an air pump and a fan.
  • an air pump is provided in the exhaust pipe 22 .
  • the exhaust apparatus 17 of the present Embodiment is controlled such that the exhaust gas in the sterilizing chamber 10 is exhausted at once.
  • the apparatus may be controlled such that the gas is exhausted to the buffer portion 14 in multiple times. In this manner, in the case the exhaust gas is supplied to the exhaust gas treatment means 15 in multiple times, it is advantageous that the exhaust gas can be reliably made to be harmless.
  • the chamber 1 of the NO 2 gas supply system and the exhaust system is connected by a bypass pipe 25 provided with a third open/closure device 24 .
  • a third open/closure device 24 By opening the third open/closure device 24 , an exhausting step in which the inside of the chamber 1 is vacuumed can be performed by driving the exhaust apparatus 17 of the exhaust system.
  • NO 2 gas remaining in the chamber 1 is made to be harmless by the exhaust system to safely exhaust.
  • the sterilizing apparatus is configured in which one sterilizing chamber 10 and exhaust system are linked via the exhaust pipe 22 .
  • a multiple type apparatus in which exhaust pipes 22 from a plurality of sterilizing chambers 10 are linked to a single exhaust system may be provided, and the exhaust system which is only required at the time of exhausting the exhaust gas may be controlled such that the system is driven while being shared. Since a shared exhaust system can serve relative to multiple sterilizing chambers 10 , there is no unnecessary part as a whole sterilizing apparatus and the apparatus can be made to be compact.
  • the sterilization method including the following steps:
  • the shielding door of the sterilizing chamber 10 is opened, and the item to be sterilized is placed by inserting it from the opening to the inside.
  • the item to be sterilized may be suitably placed on a placement table in accordance with its shape.
  • shelves may be arranged in such a manner that they do not overlap each other, and the items are placed thereon.
  • the pressure of the inside of the sterilizing chamber 10 is decreased through exhausting the air in the chamber by driving an air pump of the exhaust apparatus. Through this depressurization, the air in detailed and innermost portions such as a hole of the item to be sterilized is discharged.
  • the NO 2 gas thus quickly enters into the innermost detailed portions such as a hole of the item to be sterilized. As a result, the reliability of sterilization increases.
  • the humidifying step is performed by supplying vapors in the sterilizing chamber 10 using the humidifying apparatus 26 provided at the sterilizing chamber 10 .
  • the vapors penetrate into the innermost detail portions of such as a hole of the item to be sterilized through the humidifying step, and the high concentration NO 2 gas is filled under this state.
  • Suitable humidity and NO 2 concentration for sterilization are achieved in the detailed and innermost portions of the item to be sterilized, and the reliability of the sterilization is preferably increased as a result.
  • the combination of the sufficient humidity and NO 2 concentration facilitates the generation of nitric acid on the surface of germs, and increases the sterilizing effect.
  • the high concentration NO 2 gas is filled after the humidification in the present Embodiment.
  • the NO 2 enters into the detailed and innermost portions of the already humidified item to be sterilized and is quickly converted to nitric acid.
  • the sterilization effect is effectively achieved.
  • the humidification is performed under the decreased pressure through the evacuation. It is preferable that the generation of the vapors is therefore obtained in the humidifying apparatus 26 at a relatively low temperature, and vapors quickly enter into the detailed portions of the item to be sterilized.
  • the supplying step by firstly driving the NO 2 gas system, the high concentration NO 2 gas stored in the chamber 1 is sucked by the negative pressure in the sterilizing chamber 10 whose pressure has been decreased by the vacuuming step.
  • the high concentration NO 2 gas passes through the supply pipe 10 a with the opened first open/closure device 10 b to be supplied to the sterilizing chamber 10 .
  • the first open/closure device 10 b is closed.
  • the chamber 1 and the exhausting system communicate via the bypass pipe 25 by opening the third open/closure device 24 .
  • the exhaust apparatus 17 of the exhaust system air pump
  • the NO 2 gas remaining in the chamber 1 is sucked and is exhausted by making the gas harmless with the exhaust system.
  • the chamber 1 can be vacuumed (exhausting step) with the suction force. Therefore, in the present Embodiment, the NO 2 gas remaining in the chamber 1 can be exhausted by making the gas to be harmless, and the exhausting step (vacuuming) of the chamber 1 can be performed by the sucking function of the exhaust apparatus 17 of the same system.
  • the sterilizing apparatus organically cooperates to function as a whole.
  • the microwave generating apparatus 2 a of the plasma generator 2 and the pressure device 6 are stared. With that, the gas mixture circulates in the circulating path 4 , and nitrogen and oxygen of the gas mixture are displaced to the low-temperature plasma state in the plasma generating portion 2 c of the plasma generator 2 . As a result, nitrogen oxides such as nitrogen monoxide and nitrogen dioxide, and ozone are generated to generate an NOx gas mixture.
  • the NOx gas mixture By further circulating the NOx gas mixture, the NO 2 concentration is gradually increased as mentioned above, and the high concentration NO 2 gas with the NO 2 concentration of from 5,000 to 100,000 ppm is generated.
  • the high concentration NO 2 gas generated in the circulating step is supplied to the sterilizing chamber 10 by again performing the supplying step.
  • the internal pressure of the sterilizing chamber 10 with a larger volume than that of the chamber 1 which has been decreased in the vacuuming step increases, and the NO 2 concentration also gradually increases.
  • the NO 2 concentration in the sterilizing chamber 10 is adjusted to be from 9 to 100 mg/L, more preferably from 20 to 80 mg/L, and 20 to 40 mg/L in the present Embodiment.
  • the sterilizing step the item to be sterilized loaded by the setting step is maintained for a certain period of time in the sterilizing chamber 10 filled with the NO 2 gas with the predetermined NO 2 concentration.
  • the duration for sterilization is different depending on the factors such as the NO 2 concentration in the sterilizing chamber 10 and types of items to be sterilized, the sterilization is preferably maintained from 10 to 480 minutes. In the case the duration is less than 10 minutes, a sufficient sterilization effect required for any germs may not be obtained. On the other hand, in the case the duration is over 480 minutes, there is no significant difference in sterilization effect over such duration, and the processing time is likely to be unnecessarily prolonged.
  • the second open/closure device 23 is opened and the exhaust apparatus 17 of the exhausting system is driven.
  • the used high concentration NO 2 gas exhaust gas
  • the exhaust gas remaining in the sterilizing chamber 10 is sucked and exhausted in part, i.e. approximately 3 to 10 times, with the predetermined NO 2 gas contents in accordance with the processing capacity of the gas treatment means 15 .
  • the exhaust gas treatment means does not need to be excessively configured even for the exhaust gas with high concentration NO 2 , and the exhaust gas can be reliably made to be harmless.
  • the exhaust apparatus 17 is driven while the first open/closure device is closed and the second open/closure device is open to exhaust a certain amount of high concentration NO 2 gas in the sterilizing chamber to the exhaust gas treatment means 15 such that the pressure of the sterilizing chamber 10 is made to be negative. Subsequently, by opening the first open/closure device and closing the second open/closure device, the high concentration NO 2 gas remaining in the chamber 1 is sucked to the sterilizing chamber 10 by the negative pressure. It is possible that, by repeating the procedure for multiple times, the exhaust gas remaining in the sterilizing chamber 10 and chamber 1 is made to be harmless for exhaustion.
  • the high concentration NO 2 gas was prepared by the NO 2 gas supply system.
  • the air (dew point: ⁇ 60° C.) was used as an ingredient, and plasma lightning time in the plasma generator was 25 minutes.
  • the concentration of the generated high concentration NO 2 was 47 kppm, and the gas was stored in the chamber.
  • the pressure at this time in terms of the differential pressure from the atmospheric pressure (101 kPa (absolute pressure)), was ⁇ 5 kPa (relative pressure).
  • ozone with 40 kppm was prepared using the air as an ingredient.
  • the prepared ozone was introduced in the ozone chamber to perform substitution until the concentration of ozone reached 40 kppm.
  • the exhaustion was started by opening the third open/closure device. After the high concentration NO 2 gas was passed through a particle filter (SFB200, manufactured by SMC Corporation) and a silica gel layer (silica gel A type 5UP, manufactured by Tokai Chemical Industry Co., Ltd.), the gas was adjusted by an exhaust gas flow meter (8550, manufactured by Kojima Instruments Inc.) such that the composition ratio relative to ozone was to be 2:1.
  • a particle filter SMC Corporation
  • silica gel layer sica gel A type 5UP, manufactured by Tokai Chemical Industry Co., Ltd.
  • the ozone was mixed with the above-described high concentration NO 2 gas, the flow of which had been adjusted, such that the composition ratio was to be 2:1.
  • the mixing of the high concentration NO 2 gas and ozone was performed in the buffer portion (buffer tank).
  • the gas mixture including dinitrogen pentoxide was passed through two nitric acid adsorption catalyst (ADS55, manufactured by Adsorption Technology Industries, Ltd.) disposed in serial.
  • the concentration of the high concentration NO 2 gas generated in the NO 2 gas supply system was made to be 44 kppm, and the composition ratio of the high concentration NO 2 gas and ozone in the exhausting step was made to be 5:2, the high concentration NO 2 gas was processed in the same manner as Example 1 to measure the concentration of the remaining NOx. The results are shown in Table 1.
  • the concentration of the high concentration NO 2 gas generated in the NO 2 gas supply system was made to be 50 kppm, and the composition ratio of the high concentration NO 2 gas and ozone in the exhausting step was made to be 3:1, the high concentration NO 2 gas was processed in the same manner as Example 1 to measure the concentration of the remaining NOx. The results are shown in Table 1.
  • Example 1 where the composition ratio of the high concentration NO 2 and ozone is 2:1, the NOx was completely absorbed in all cases when the internal pressures of the chamber were from ⁇ 50 to ⁇ 90 kPa (relative pressure).
  • Example 2 where the composition ratio of the high concentration NO 2 and ozone is 5:2, the NOx was also completely absorbed in all cases when the internal pressures of the chamber were from ⁇ 50 to ⁇ 90 kPa (relative pressure).
  • Example 3 where the composition ratio of the high concentration NO 2 and ozone is 3:1, the NOx was completely absorbed in cases when the internal pressures of the chamber were from ⁇ 50 to ⁇ 85 kPa (relative pressure). However, a portion of NOx was not absorbed and remaining when the internal pressures of the chamber were ⁇ 90 kPa (relative pressure).
  • % Ratio of NO 2 refers to a ratio of the high concentration NO 2 gas in the gas mixture of the high concentration NO 2 gas and ozone (theoretical value). In those Examples, a portion (25%) of the high concentration NO 2 gas is consumed by passing through the silica gel layer before being mixed with ozone. Thus, a ratio of the high concentration NO 2 gas in the gas mixture of the high concentration NO 2 gas and ozone (theoretical value) is calculated in “% Ratio of NO 2 (after conversion)”. Specifically, in terms of Example 1, the following calculations were performed.
  • the sterilizing apparatus using the exhaust system, and the sterilizing method using the sterilizing apparatus of the present invention as a result of adsorbing NO 2 in a high concentration NO 2 gas used in a sterilization process and ozone, and generating nitric acid or dinitrogen pentoxide by accelerating the chemical reaction of the adsorbed NO 2 and ozone and retaining the resultant, the exhaust gas can be reliably and efficiently made to be harmless even if a concentration thereof is high.
  • NO 2 in the exhaust gas exhausted from the sterilizing apparatus can be removed.
  • high concentration NO 2 gas can be completely absorbed and exhausted after making the gas to be harmless.

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US10905786B2 (en) 2017-03-27 2021-02-02 Regeneron Pharmaceuticals, Inc. Sterilisation method
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JP6085446B2 (ja) * 2012-10-15 2017-02-22 立山マシン株式会社 滅菌方法
KR101740016B1 (ko) * 2015-04-14 2017-05-25 한국기계연구원 플라즈마 증발기 및 이를 이용하는 배기가스 제거 시스템
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US11766494B2 (en) * 2020-03-27 2023-09-26 Miura Co., Ltd. Sterilizing method and sterilizer
CN114796580A (zh) * 2022-05-18 2022-07-29 山东杰普特净化设备有限公司 一种医用负压站房排气口专用废气消毒灭菌装置

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